Thermodynamics

Lecture 2 – Heat and the First

Law of Thermodynamics
State Variables
 State variables describe the state of a system
 In the macroscopic approach to
thermodynamics, variables are used to
describe the state of the system
 Pressure, temperature, volume, internal energy
 These are examples of state variables
 They are linked by the Equation of State PV = nRT
 The macroscopic state of an isolated system
can be specified only if the system is in
thermal equilibrium internally
Transfer Variables
 The quantities Q and W are called transfer
variables.
 Transfer variables are zero unless a process
occurs in which energy is transferred across
the boundary of a system
 Transfer variables are only associated with
changes in the state of the system, not the
states themselves.
 Example of heat: we can only assign a value of
the heat if energy crosses the boundary by heat
 Work in Thermodynamics
 Work can be done on a deformable system,
such as a gas, as we can apply a force in
which the system changes a dimension, ie
there is a change in distance in the direction
of the force
 We cannot do work on a stiff (non-
deformable) body. Why?
 Consider a cylinder with a moveable piston
 A force is applied to slowly compress the gas
 The compression is slow enough for all
the system to remain essentially in
thermal equilibrium
 This is said to occur quasi-statically
Work, 2
 The piston is pushed downward by a
force F through a displacement of dr:
dW  F  dr   Fˆj  dyˆj   Fdy   PA dy
 A.dy is the change in volume of the gas,
dV
 Therefore, the work done on the gas is
dW = -P dV
Work, 3
 Interpreting dW = - P dV
 If the gas is compressed, dV is negative
and the work done on the gas is positive
 If the gas expands, dV is positive and the
work done on the gas is negative
 If the volume remains constant, the work
done is zero
Vf
 The total work done is: W   Vi
P dV
 PV Diagrams
 PV diagrams are used when
the pressure and volume are
known at each step of the
process
 The state of the gas at each
step can be plotted on a
graph called a PV diagram
 This allows us to visualize the
process through which the gas
is progressing
 The curve is called the path
PV Diagrams, cont
 The work done on a gas in a quasi-
static process that takes the gas from
an initial state to a final state is the
negative of the area under the curve on
the PV diagram, evaluated between the
initial and final states
 This is true whether or not the pressure
stays constant
 The work done does depend on the path
taken
 Work Done By Various Paths

 Each of these processes has the same initial

and final states
 The work done differs in each process
 The work done depends on the path
Work From a PV Diagram,
Example 1
 The volume of the
gas is first reduced
from Vi to Vf at
constant pressure Pi
 Next, the pressure
increases from Pi to
Pf by heating at
constant volume Vf
 W = -Pi (Vf – Vi)
 Work From a PV Diagram,
Example 2
 The pressure of the
gas is increased from
Pi to Pf at a constant
volume
 The volume is
decreased from Vi to
Vf
 W = -Pf (Vf – Vi)
 Work From a PV Diagram,
Example 3
 The pressure and the
volume continually change
 The work is some
intermediate value
between –Pf (Vf – Vi) and
–Pi (Vf – Vi)
 To evaluate the actual
amount of work, the
function P (V ) must be
known
 Heat Transfer, Example 1
 The energy transfer, Q, into or
out of a system also depends on
the process
 The energy reservoir is a
source of energy that is
considered to be so great that a
finite transfer of energy does
not change its temperature
 The piston is pushed upward,
the gas is doing work on the
piston
 Heat Transfer, Example 2
 This gas has the same initial
volume, temperature and
pressure as the previous
example
 The final states are also
identical
 No energy is transferred by
heat through the insulating
wall
 No work is done by the gas
expanding into the vacuum
Energy Transfer, Summary
 Energy transfers by heat, like the work
done, depend on the initial, final, and
intermediate states of the system
 Both work and heat depend on the path
taken
 Neither can be determined solely by the
end points of a thermodynamic process
The First Law of
Thermodynamics
 The First Law of Thermodynamics is a special
case of the Law of Conservation of Energy
 It takes into account changes in internal energy
and energy transfers by heat and work
 Although Q and W each are dependent on the
path, Q + W is independent of the path
 The First Law of Thermodynamics states that
DEint = Q + W
 All quantities must have the same units of measure
of energy
The First Law of
Thermodynamics, cont
 One consequence of the first law is that there
must exist some quantity known as internal
energy which is determined by the state of
the system
 For infinitesimal changes in a system dEint =
dQ + dW
 The first law is an energy conservation
statement specifying that the only type of
energy that changes in a system is internal
energy
Isolated Systems
 An isolated system is one that does not
interact with its surroundings
 No energy transfer by heat takes place
 The work done on the system is zero
 Q = W = 0, so DEint = 0
 The internal energy of an isolated
system remains constant
Cyclic Processes
 A cyclic process is one that starts and ends in the
same state
 This process would not be isolated
 On a PV diagram, a cyclic process appears as a
closed curve
 The change in internal energy must be zero since
it is a state variable
 If DEint = 0, Q = -W
 In a cyclic process, the net work done on the
system per cycle equals the area enclosed by the
path representing the process on a PV diagram
 Adiabatic Process
 An adiabatic process is one
during which no energy
enters or leaves the system
by heat
 Q=0
 This is achieved by:
 Thermally insulating the walls of
the system
 Having the process proceed so
quickly that no heat can be
exchanged
Adiabatic Process, cont
 Since Q = 0, DEint = W
 If the gas is compressed adiabatically,
W is positive so DEint is positive and the
temperature of the gas increases
 If the gas expands adiabatically, the
temperature of the gas decreases
Adiabatic Processes, Examples
 Some important examples of adiabatic
processes related to engineering are:
 The expansion of hot gases in an internal
combustion engine
 The liquefaction of gases in a cooling
system
 The compression stroke in a diesel engine
 Adiabatic Free Expansion
 This is an example of adiabatic
free expansion
 The process is adiabatic because
it takes place in an insulated
container
 Because the gas expands into a
vacuum, it does not apply a force
on a piston and W = 0
 Since Q = 0 and W = 0, DEint = 0
and the initial and final states are
the same
 No change in temperature is
expected
Isobaric Processes
 Here pressure is held constant
 The values of the heat and the work are
generally both nonzero
 The work done is the area under the
curve in the PV diagram, given simply
by
W = P (Vf – Vi) where P is the
constant pressure
Isovolumetric Processes
 Here the volume is fixed
 Since the volume does not change, W =
0
 From the first law, DEint = Q
 If energy is added by heat to a system
kept at constant volume, all of the
transferred energy remains in the
system as an increase in its internal
energy
Isothermal Process
 Here the temperature is constant
 Since there is no change in
temperature, DEint = 0
 Therefore, Q = - W
 Any energy that enters the system by
heat must leave the system by work
 Isothermal Process, cont
 At right is a PV
diagram of an
isothermal expansion
 The curve is a
hyperbola
 The curve is called an
isotherm
Isothermal Expansion, Details
 The curve of the PV diagram indicates
PV = constant
 The equation of a hyperbola
 Because it is an ideal gas and the
process is quasi-static, PV = nRT and
Vf Vf nRT V f dV
W    P dV    dV  nRT 
Vi Vi V Vi V

 Vi 
W  nRT ln  
 Vf
 
Special Processes, Summary
 Adiabatic
 No heat exchanged
 Q = 0 and DEint = W
 Isobaric
 Constant pressure
 W = P (Vf – Vi) and DEint = Q + W
 Isothermal
 Constant temperature
 DEint = 0 and Q = -W